The reaction of a fluorinated β-aminoimine compound ArN]C(Me)CH]C(Me)NHAr (1) (Ar = 2,6-F 2 C 6 H 3 ) with n-BuLi in coordinating solvents (Et 2 O and THF) leads to the solvated complexes [HC(CMeNAr) 2 ]Li(Et 2 O) (2) and [HC(CMeNAr) 2 ]Li(THF) (3), respectively. They exist as momonuclear complexes featuring lithium atoms in a distorted trigonal planar environment. The same reaction, which was then carried out in a non-coordinated solvent (pentane), provided complex [HC(CMeNAr) 2 ] 2 Li 2 (4). It crystallized as a dinuclear complex in the solid state, featuring lithium atoms in a pseudo-tetrahedral coordination environment. Notably, one fluorine atom of each ligand was involved to stabilize the lithium center. Taking complex 2 as the precursor, a series of group 12 metal complexes were prepared via the reaction with MX 2 (M = Zn, Cd, Hg; X = Br, I). The diketiminate zinc complexes [HC(CMeNAr) 2 ]Zn(μ-I) 2 Li(Et 2 O) 2 (5) and [HC(CMeNAr) 2 ]Zn(μ-Br) 2 Li(Et 2 O) 2 (6) were successfully synthesized and characterized by single crystal X-ray diffraction analysis. When 2 reacted with CdI 2 , the expected double iodide bridging product [HC(CMeNAr) 2 ]Cd(μ-I) 2 Li(Et 2 O) 2 (7a) was only generated in a small amount, with the single iodide bridging complex {HC(CMeNAr) 2 }Cd(I)(μ-I)Li(Et 2 O) 3 (7b) as the major product. These results were unambiguously confirmed by NMR spectroscopy and X-ray crystallography. Next, a mercury complex [HC(CMeNAr) 2 ]Hg(μ-I) 2 Li(Et 2 O) (8) was prepared by using HgI 2 as the metal source. Additionally, [HC(CMeNAr) 2 ]ZnEt (9) was also obtained by mixing ligand 1 with Et 2 Zn.